EP0068540B1 - Procédé pour séparer du germanium d'une solution aqueuse à l'aide d'un alpha-hydroxyoxime - Google Patents

Procédé pour séparer du germanium d'une solution aqueuse à l'aide d'un alpha-hydroxyoxime Download PDF

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Publication number
EP0068540B1
EP0068540B1 EP82200685A EP82200685A EP0068540B1 EP 0068540 B1 EP0068540 B1 EP 0068540B1 EP 82200685 A EP82200685 A EP 82200685A EP 82200685 A EP82200685 A EP 82200685A EP 0068540 B1 EP0068540 B1 EP 0068540B1
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EP
European Patent Office
Prior art keywords
germanium
organic phase
aqueous
phase
organic
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP82200685A
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German (de)
English (en)
French (fr)
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EP0068540A1 (fr
Inventor
Achille De Schepper
Marc Coussement
Antoine Van Peteghem
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Metallurgie Hoboken-Overpelt SA
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Metallurgie Hoboken-Overpelt SA
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G17/00—Compounds of germanium
    • C01G17/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40—Mixtures
    • C22B3/406—Mixtures at least one compound thereof being a heterocyclic compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • US Pat. No. 3,883,634 relate to the recovery of germanium from aqueous solutions containing Ge, As, Zn, Ni, Cu, Fe, C1, and from 130 to 460 g / I of H 2 SO 4 , an organic liquid is used for the extraction of germanium consisting either of undiluted LIX-63, or of LIX-63 diluted with 50% of kerosene, or of LIX-63 diluted with 30% of kerosene; the germanium is re-extracted from the organic liquid charged with germanium, using an aqueous solution of NaOH at 175 g / l.
  • the object of the present invention is to provide a process as defined above, which lends itself much better than the aforementioned known process for the treatment of aqueous Germaniferous solutions with low acidity and which lends itself even better than this known process for the treatment of Germanic aqueous solutions with high acidity.
  • an 8-hydroxyquinoline substituted with at least one hydrocarbon group is added to the organic liquid.
  • Such a compound corresponds to the general formula: wherein R is hydrogen or a hydrocarbon group such as alkyl, alkenyl, cycloaliphatic, aryl or a combination thereof (e.g. alkaryl, aralkenyl, alkylcycloalkyl, aralkyl, etc.), at least one of the substituents R being such a hydrocarbon group.
  • R is hydrogen or a hydrocarbon group such as alkyl, alkenyl, cycloaliphatic, aryl or a combination thereof (e.g. alkaryl, aralkenyl, alkylcycloalkyl, aralkyl, etc.), at least one of the substituents R being such a hydrocarbon group.
  • the 7-alkenyl-8-hydroxyquinolines are the most interesting.
  • a concentration of 1 g / I of Ge in the aqueous phase is in equilibrium with a concentration of 0.625 g / I of Ge in the organic phase in the first case (curve 1), with a concentration of 1.63 g / I of Ge in the organic phase in the second case (curve 2) and with a concentration of 3.55 g / I of Ge in the organic phase in the third case (curve 3).
  • step a part of the acid contained in the starting germaniferous aqueous solution is coextracted with germanium by the organic liquid in step a, if this organic liquid is not previously acidified, that is ie brought into contact with an acid solution.
  • the germanium-depleted aqueous phase produced in step a therefore has a lower acidity than the starting aqueous solution, if the organic liquid has not been acidified beforehand.
  • step a it is advantageous to ensure that the acidity of the germanium-depleted aqueous phase produced in step a (and separated in step b) is not less than 0.1 N because, otherwise, the germanium extraction yield becomes low.
  • a very high acidity for example 8N, does not hinder in step a. It is therefore possible to treat, by the process of the present invention, very acidic germaniferous aqueous solutions.
  • the only drawback that the treatment of very acidic solutions entails lies in the fact that much acid must subsequently be neutralized in step c. For this reason, it is not advisable to use an aqueous starting solution whose acidity is greater than 2N, unless the conditions for preparing the starting solution, for example by leaching of a germaniferous material, do not impose an acidity higher than 2N.
  • step b and c It is very useful to provide a washing operation between steps b and c, which consists in bringing the organic phase loaded with germanium into contact with water. Part of the acid which it contains and which otherwise would have had to be neutralized in step c is thus re-extracted from the organic phase.
  • germaniferous organic phase contains impurities such as iron and arsenic, part of these impurities are also re-extracted.
  • This washing operation therefore produces, on the one hand, a partially deacidified and partially purified Germaniferous organic phase and, on the other hand, an impure acidic aqueous phase.
  • the organic phase is sent to step c and the aqueous phase can be added to the starting solution which must still go through step a.
  • the germanium-depleted organic phase which results from stage d and which may still contain impurities such as Fe can be recycled as such to stage a.
  • a preferred embodiment of the method of the invention is illustrated by the diagram in FIG. 2 attached. It essentially comprises the following liquid-liquid extraction operations: the extraction of germanium from the starting solution, the washing of the germaniferous organic phase, the re-extraction of germanium from the washed germaniferous organic phase and the acidification of the organic phase discharged.
  • Each of these operations can be carried out in a traditional liquid-liquid extraction apparatus, for example in a mixer-settler when the operation is completed. carried out in one stage or in a bank of mixer-settlers when the operation is carried out in several stages.
  • the process of the present invention is particularly useful for treating aqueous Germaniferous solutions which are practically free of copper, i.e. solutions which contain less than 0.1 g / I and preferably less 0.01 g / I Cu, since the licensee has found that copper constitutes a poison for ⁇ -hydroxyoxime in the sense that copper is fixed by ⁇ -hydroxyoxime in both acidic and in basic medium, which means that it can no longer be separated from ⁇ -hydroxyoxime.
  • copper constitutes a poison for ⁇ -hydroxyoxime in the sense that copper is fixed by ⁇ -hydroxyoxime in both acidic and in basic medium, which means that it can no longer be separated from ⁇ -hydroxyoxime.
  • To treat aqueous Germaniferous solutions having a substantial copper content it is therefore recommended to use the process which is the subject of the above-mentioned European patent application.
  • This example relates to the separation of germanium from an aqueous solution containing (in g / I): 3.5 Ge; 0.8 As; 1.5 Fe 3+ ; 50 H 2 SO 4 .
  • the organic liquid consists of 99% by volume of LIX-63 and 1% by volume of LIX-26 and it contains 4.5 g / l of H 2 SO 4 .
  • Germanium is extracted against the current, in 4 stages and with a volumetric ratio between the organic phase and the aqueous phase (hereinafter referred to as O: A ratio) of 1: 1.
  • the organic phase contains (in g / I): 3.49 Ge; 0.2 As; 0.4 Fe 3+ ; 3 H 2 SO 4 .
  • the raffinate contains (in g / I): 0.005 Ge; 0.6 As; 1.1 Fe 3+ ; 51.5 H 2 SO 4 .
  • the germaniferous organic phase is washed with water. This operation is carried out against the current, in 2 stages, and with an O: A ratio of 10: 1.
  • the washed Germaniferous organic phase contains (in g / I): 3.37 Ge; 0.05 As; 0.31 Fe 3+ ; 0.5 H 2 SO 4 .
  • the acidic wash water contains (in g / I): 1.2 Ge; 1.5 As; 0.9 Fe; 25 H 2 SO 4 .
  • germanium is re-extracted from the organic phase. germaniferous washed with an aqueous NaOH solution at 150 g / I. This operation is carried out against the current, in 5 stages, and with an O: A ratio of 10: 1.
  • the organic phase discharged of germanium contains (in g / 1): 0.015 Ge; 0 As; 0.31 Fe 3+ .
  • the germanium eluate contains (in g / I): 33.69 Ge; 0.5 As; 0 Fe 3+ .
  • the organic phase discharged from germanium is acidified with an aqueous solution of H 2 SO 4 at 250 g / I, in a single stage, and with an O: A ratio of 5: 1.
  • the regenerated organic phase contains (in g / 1): 0.015 Ge; 0.01 Fe 3+ ; 4.5 H 2 SO 4 .
  • the impure aqueous solution contains (in g / I): 0.001 Ge; 1.5 Fe 3+ ; 150 H 2 SO 4 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP82200685A 1981-06-22 1982-06-04 Procédé pour séparer du germanium d'une solution aqueuse à l'aide d'un alpha-hydroxyoxime Expired EP0068540B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
LU83449 1981-06-22
LU83449A LU83449A1 (fr) 1981-06-22 1981-06-22 Procede pour separer du germanium d'une solution aqueuse a l'aide d'un alpha-hydroxyoxime

Publications (2)

Publication Number Publication Date
EP0068540A1 EP0068540A1 (fr) 1983-01-05
EP0068540B1 true EP0068540B1 (fr) 1985-01-16

Family

ID=19729676

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EP82200685A Expired EP0068540B1 (fr) 1981-06-22 1982-06-04 Procédé pour séparer du germanium d'une solution aqueuse à l'aide d'un alpha-hydroxyoxime

Country Status (6)

Country Link
US (1) US4432952A (xx)
EP (1) EP0068540B1 (xx)
JP (1) JPS589817A (xx)
CA (1) CA1187707A (xx)
DE (1) DE3261931D1 (xx)
LU (1) LU83449A1 (xx)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1220035A (en) * 1984-02-02 1987-04-07 Cominco Ltd. Recovery of germanium from aqueous solutions
DE3508041A1 (de) * 1985-03-07 1986-09-11 Preussag Ag Metall, 3380 Goslar Verfahren zur fluessig-fluessig-extraktion von gallium, germanium oder indium aus waessrigen loesungen
DE3635450A1 (de) * 1986-10-18 1988-04-21 Metallgesellschaft Ag Verfahren zur selektiven gewinnung von germanium und/oder arsen aus waessrigen loesungen
AT388570B (de) * 1986-11-07 1989-07-25 Bleiberger Bergwerks Union Ag Extraktionsmittel sowie verfahren zur aufarbeitung von ge-haeltigen waesserigen loesungen durch fluessig/fluessigextraktion
DE3719437A1 (de) * 1987-06-11 1988-12-22 Hoechst Ag Verfahren zur gewinnung von gallium aus basisch waessrigen natriumaluminatloesungen durch fluessig-fluessigextraktion
ES2004642A6 (es) * 1987-07-15 1989-01-16 Asturiana De Zinc Sa Procedimiento para la recuperacion de recuperacion de germanio de soluciones que lo contienen
US4915919A (en) * 1987-09-29 1990-04-10 Cominco Ltd. Recovery of germanium from aqueous solutions by solvent extraction
LU87108A1 (fr) * 1988-01-18 1989-08-30 Metallurgie Hoboken Procede d'extraction de metal
BE1002453A3 (nl) * 1989-04-28 1991-02-12 Acec Union Miniere Werkwijze voor het winnen van germanium.
US5277882A (en) * 1989-04-28 1994-01-11 Union Miniere S.A. Process for recovering germanium
CN112662899B (zh) * 2020-12-10 2022-11-22 衢州华友钴新材料有限公司 一种用Lix-63为主的多元协萃体系从高砷高硅硫酸盐溶液中选择性萃取分离锗的方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637711A (en) * 1968-03-25 1972-01-25 Ashland Oil Inc Beta-alkenyl substituted 8-hydroxyquinolines
LU67596A1 (xx) * 1973-05-14 1975-03-06
CA1052585A (en) * 1974-03-04 1979-04-17 Robert B. Sudderth Liquid ion exchange extraction of zinc
GB1486057A (en) * 1975-06-09 1977-09-14 Ici Ltd Hydroxyphenyl tetrazoles and their use in the extraction of metals
BE881273Q (fr) * 1980-01-22 1980-05-16 Metallurgie Hoboken Procede d'extraction liquide-liquide du germanium
US4389379A (en) * 1980-08-15 1983-06-21 Societe Miniere Et Metallurgique De Penarroya Process for selective liquid-liquid extraction of germanium

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 81, 1974, page 265, no. 17259m, Columbus Ohio (USA); N.P. RUDENKO et al.: "Extraction of germanium (IV) 8-hydroxyquinolinate with mixed solvents" *
J. INORG. NUCL. CHEM., vol. 41, 1979, pages 1353-1363, Pergamon Press Ltd., (GB); B. MARCHON et al.: "Some typical behaviours of the beta-dodecenyl-8-gydroxyquinoline through its reactions with germanium (IV)" *

Also Published As

Publication number Publication date
EP0068540A1 (fr) 1983-01-05
CA1187707A (en) 1985-05-28
JPH0210765B2 (xx) 1990-03-09
DE3261931D1 (en) 1985-02-28
LU83449A1 (fr) 1983-04-06
US4432952A (en) 1984-02-21
JPS589817A (ja) 1983-01-20

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